CnTAB/polystyrene sulfonate mixtures at air–water interfaces: effects of alkyl chain length on surface activity and charging state

Literature Information

Publication Date 2019-03-27
DOI 10.1039/C9CP01107B
Impact Factor 3.676
Authors

Felix Schulze-Zachau, Björn Braunschweig


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Abstract

Binding and phase behavior of oppositely charged polyelectrolytes and surfactants with different chain lengths were studied in aqueous bulk solutions and at air–water interfaces. In particular, we have investigated the polyanion poly(sodium 4-styrenesulfonate) (NaPSS) and the cationic surfactants dodecyltrimethylammonium bromide (C12TAB), tetradecyltrimethylammonium bromide (C14TAB) and cetyltrimethylammonium bromide (C16TAB). In order to reveal the surfactant/polyelectrolyte binding, aggregation and phase separation of the mixtures, we have varied the NaPSS concentration systematically and have kept the surfactant concentration fixed at 1/6 of the respective critical micelle concentration. Information on the behavior in the bulk solution was gained by electrophoretic mobility and turbidity measurements, while the surface properties were studied using surface tension measurements and vibrational sum-frequency generation (SFG). This has enabled us to relate bulk to interfacial properties with respect to the charging state and the surfactants’ binding efficiency. We found that the latter two are strongly dependent on the alkyl chain length of the surfactant and that binding is much more efficient as the alkyl chain length of the surfactant increases. This also results in a different phase behavior as shown by turbidity measurements of the bulk solutions. Charge neutral aggregates that are forming in the bulk adsorb onto the air–water interface – an effect that is likely caused by the increased hydrophobicity of CnTAB/PSS complexes. This conclusion is corroborated by SFG spectroscopy, where we observe a decrease in the intensity of O–H stretching bands, which is indicative of a decrease in surface charging and the formation of interfaces with negligible net charge. Particularly at mixing ratios that are in the equilibrium two-phase region, we observe weak O–H intensities and thus surface charging.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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